Smectics, ferroelectricity

Yoshino et al. [358] have investigated a derivative with mesogenic ester groups, poly(bis(4-methoxy-4 -hcxyloxy biphenyl) dipropargyl malonate), and find electrochemical doping with BF4to occur to both the main chain and the mesogenic unit in the side chain. The x-ray diffraction indicates a smectic phase between 80 and 115°C. The formation of a layered structure in a mixture of the polymer with a smectic ferroelectric liquid crystal is also reported. 

In the most simple chiral polar tilted smectics, ferroelectric liquid crystals, the flexoelectric phenomenon influences the structure of the SmC phase only quantitatively. It affects the elastic and chiral couplings and consequently slightly changes the transition temperature to the tilted phase and the pitch of the helicoidal modulation. 

Chiral smectic ferroelectric liquid crystals are liquids that possess spontaneous polar order. Combined with their excellent processibility on silicon integrated circuits, these liquid crystals provide an attractive potential approach to synthesis of materials for second order nonlinear optics, provided adequate second order susceptibility can be obtained. Unfortunately, the second-order nonlinear optical susceptibility of the ferroelectric liquid crystals are usually low and their thermal stability is limited. Several, very interesting approaches to utilization of liquid crystals, however, were carried out. 

Finally the three remaining Chapters 10-12 are devoted to optics and electrooptics of, respectively, nematic, cholesteric and smectic (ferroelectric and antiferro-electric) phases. In contrast to my earlier book published by WUey in 1983, only the most principal effects have been considered and the discussion of the underlying principles is much more detailed. 

Conoscopy is used to study the field-induced effects in nematic and smectic ferroelectrics. It is most useful when one has a large domain with uniform director orientation without any structure in the lateral direction. For example, with orthoscopy one cannot distinguish between truly and quasi-isotropic (homeotropic) situahons. However, with conoscopy one can easily see the difference in the case of isotropic director structure one sees only... 

Chapters 1-5 cover the basic physics and optical properties of liquid crystals intended for beginning workers in liquid crystal related areas. Although the major focus is on nematics, we have included sufficient discussions on other mesophases of liquid crystals such as the smectics, ferroelectrics, and cholesterics to enable the readers to proceed to more advanced or specialized topics elsewhere. New sections have also been added. For example, in Chapter 4, a particularly important addition is a quantitative discussion of the optical properties and fundamentals of one-dimensional photonic crystal band stractures. Dispersion is added to fill in an important gap in most treatments of cholesteric liqrrid crystals. 

As witli tlie nematic phase, a chiral version of tlie smectic C phase has been observed and is denoted SniC. In tliis phase, tlie director rotates around tlie cone generated by tlie tilt angle [9,32]. This phase is helielectric, i.e. tlie spontaneous polarization induced by dipolar ordering (transverse to tlie molecular long axis) rotates around a helix. However, if tlie helix is unwound by external forces such as surface interactions, or electric fields or by compensating tlie pitch in a mixture, so tliat it becomes infinite, tlie phase becomes ferroelectric. This is tlie basis of ferroelectric liquid crystal displays (section C2.2.4.4). If tliere is an alternation in polarization direction between layers tlie phase can be ferrielectric or antiferroelectric. A smectic A phase foniied by chiral molecules is sometimes denoted SiiiA, altliough, due to the untilted symmetry of tlie phase, it is not itself chiral. This notation is strictly incorrect because tlie asterisk should be used to indicate the chirality of tlie phase and not tliat of tlie constituent molecules. 

Rieker T P, Clark N A, Smith G S, Parmar D S, Sirota E B and Safinya C R 1987 Chevron local layer structure in surface-stabilized ferroelectric smectic-C cells Phys.Rev.Lett 59 2658-61... 

Chiral Smectic. In much the same way as a chiral compound forms the chiral nematic phase instead of the nematic phase, a compound with a chiral center forms a chiral smectic C phase rather than a smectic C phase. In a chiral smectic CHquid crystal, the angle the director is tilted away from the normal to the layers is constant, but the direction of the tilt rotates around the layer normal in going from one layer to the next. This is shown in Figure 10. The distance over which the director rotates completely around the layer normal is called the pitch, and can be as small as 250 nm and as large as desired. If the molecule contains a permanent dipole moment transverse to the long molecular axis, then the chiral smectic phase is ferroelectric. Therefore a device utilizing this phase can be intrinsically bistable, paving the way for important appHcations. 

Examples of chiral smectic Chquid crystals range from 2-methylbutyl (3 -4- -decyloxybenzyhdeneaminocinnamate (12), the first ferroelectric hquid crystal discovered. 

Other more exotic types of calamitic liquid crystal molecules include those having chiral components. This molecular modification leads to the formation of chiral nematic phases in which the director adopts a natural helical twist which may range from sub-micron to macroscopic length scales. Chirality coupled with smectic ordering may also lead to the formation of ferroelectric phases [20]. 

When suitably doped, MBF can form a surface-stabilised-ferroelectric smectic-C (SSFLC) structure. Using simple assumptions regarding core orientations, Binger and Hanna are able to place an upper limit on the SSFLC cone angle for MBF of 30°. 

In this section, we will present the crystal structures of chiral mesogenic compounds exhibiting ferroelectric liquid crystalline phases which are listed in Table 18 [152-166]. Moreover, four compounds of the list show antiferroelectric properties and two compounds form only orthogonal smectic phases. The general chemical structures of the investigated chiral compounds are shown in Fig. 27. 

Zareba et al. [165] described the crystal structure of the chiral 4-(l-methyl-heptyloxycarbonyl)-phenyl 4-heptyloxytolane-4 -carboxylate (C7-tolane) which shows monotropic antiferroelectric and ferroelectric phases. The single-crystal X-ray analysis of this compound shows that the crystal has a smectic-like layer structure composed of largely bent molecules where the chain of the chiral group is almost perpendicular (86°) to the core moiety. Within the layers, the molecules are tilted. The central tolane group of the molecule is roughly planar. 

Fig. 17a-c. Sketches of the molecular arrangements for the smectic structure with alternating layer-to-layer tilt a conventional and chevron smectic C layering in low molecular mass mesogens b ferroelectric hilayer chevron structures for achiral side-chain polymers c antiferroelectric hilayer chevron structures for achiral side-chain polymers. Arrows indicate the macroscopic polarization in the direction of the molecular tilt... 

The amorphous diacrylate monomers chosen for study were two commercially available monomers, p-phenylene diacrylate (PPDA) and 1,6-hexanediol diacrylate (HDDA) (Polysciences, Inc., Warrington, PA). The liquid crystalline diacrylate studied was 1,4-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)-2-methylbenzene (C6M) (13). Chemical structures of these monomers as well as pertinent physical and LC properties are given in Figure 1. All monomers were used without further purification. The ferroelectric liquid crystal mixture consisted of a 1 1 mixture of W7 and W82 (1) (Displaytech, Boulder, CO). This mixture exhibits isotropic (I), smectic A... 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

This situation changed dramatically in 1996 with the discovery of strong electro-optic (EO) activity in smectics composed of bent-core, bowshaped, or banana-shaped achiral molecules.4 Since then, the banana-phases exhibited by such compounds have been shown to possess a rich supermolecular stereochemistry, with examples of both macroscopic racemates and conglomerates represented. Indeed, the chiral banana phases formed from achiral or racemic compounds represent the first known bulk fluid conglomerates, identified 150 years after the discovery of their organic crystalline counterparts by Pasteur. A brief introduction to LCs as supermolecular self-assemblies, and in particular SmC ferroelectric and SmCA antiferroelectric LCs, followed by a snapshot of the rapidly evolving banana-phase stereochemistry story, is presented here. 

Since P must remain normal to z and n, the polarization vector forms a helix, where P is everywhere normal to the helix axis. While locally a macroscopic dipole is present, globally this polarization averages to zero due to the presence of the SmC helix. Such a structure is sometimes termed a helical antiferroelectric. But, even with a helix of infinite pitch (i.e., no helix), which can happen in the SmC phase, bulk samples of SmC material still are not ferroelectric. A ferroelectric material must possess at least two degenerate states, or orientations of the polarization, which exist in distinct free-energy wells, and which can be interconverted by application of an electric field. In the case of a bulk SmC material with infinite pitch, all orientations of the director on the tilt cone are degenerate. In this case the polarization would simply line up parallel to an applied field oriented along any axis in the smectic layer plane, with no wells or barriers (and no hysteresis) associated with the reorientation of the polarization. While interesting, such behavior is not that of a true ferroelectric. 

Along with the prediction and discovery of a macroscopic dipole in the SmC phase and the invention of ferroelectric liquid crystals in the SSFLC system, the discovery of antiferroelectric liquid crystals stands as a key milestone in chiral smectic LC science. Antiferroelectric switching (see below) was first reported for unichiral 4-[(l-methylheptyloxy)carbonyl]phenyl-4/-octyloxy-4-biphenyl carboxylate [MHPOBC, (3)],16 with structure and phase sequence... 

Figure 8.13 Hypothetical smectic mesogen with hinge in center of core is illustrated. Such material could in principal switch to ferroelectric state, which we term the SmAPp, upon application of electric field in plane of layers. If this state exists in well on configurational hypersurface, then ground-state structure is antiferroelectric, denoted SmAPA.

By our definition, the tilt plane is normal to the polarization in the ferroelectric state in the illustration in Figure 8.13 this is a vertical plane normal to the plane of the page. Since there is no tilt of the director projected onto this plane, the phase should be considered a type of SmA. We name this structure SmAPp (an untilted polar smectic the subscript F referring to a ferroelectric structure, in this case a ferroelectric state of an antiferroelectric phase). The antiferroelectric phase is therefore also an SmA denoted SmAPA (the subscript A for antiferroelectric). While this idea is certainly intriguing, no such antiferroelectric has yet been discovered. 

Using this method, the M6R8/PM6R8 blend showed precisely the behavior expected for the achiral SmAPA structure. Specifically, the optical properties of the films were consistent with a biaxial smectic structure (i.e., two different refractive indices in the layer plane). The thickness of the films was quantized in units of one bilayer. Upon application of an electric field, it was seen that films with an even number of bilayers behaved in a nonpolar way, while films with an odd number of bilayers responded strongly to the field, showing that they must possess net spontaneous polarization. Note that the electric fields in this experiment are not strong enough to switch an antiferroelectric to a ferroelectric state. Reorientation of the polarization field (and director structure) of the polar film in the presence of a field can easily be seen, however. 

Figure 8.18 Smectic dimer of Watanabe, possessing an odd number of methylene units in linking group. This material self-assembles into intercalated smectic structure very similar to B6 banana phase. As for B6 phase, this achiral phase is also neither ferroelectric nor antiferroelectric.

The Tokyo Tech group assigned a C2 structure for the layers in the B2 phase, and ferroelectric packing of such layers to form a locally polar C2v macroscopic structure, as indicated in Figure 8.20. Other early workers in the field also adopted this structural model for the B2 phase. Brand et al. had discussed a C2 smectic chevron structure in their 1992 theoretical study,29 and while they seem to be referring to an all-anticlinic bilayer smectic, their actual graphic is basically identical to that shown in Figure 8.20. Furthermore,... 

It is interesting to point out here that with all of the theoretical speculation in the literature about polar order (both ferroelectric and antiferroelectric) in bilayer chevron smectics, and about reflection symmetry breaking by formation of a helical structure in a smectic with anticlinic layer interfaces, the first actual LC structure proven to exhibit spontaneous reflection symmetry breaking, the SmCP structure, was never, to our knowledge, suggested prior to its discovery. 

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